Vat dyestuffs of the dibenzanthrone series



Patented Aug.- 27, 1935 :VAT DYESTUFFS Hugo Wolfi, Mannheim, and Walter Mieg, ,Opladen, Germany, assignors to General Ani line Works, Inc.,'Ne'w York, N. ,Y., a corporation of Delaware N oDrawing. Application March15,--1934,' Serial ,No. 715,774. In Germany March 18, 193 3 e V o 14 Claims. (Gleam-Peri I I V i W I stuffs on vegetable fibres h'ave' froni greeiieblue 'to violet-blue, in many cases navy-blue'shades.f-

The present invention relates to sulphur containing halogenated dibenzanthrones and isodibenzanthrones and process of producing the same.

' the nature of this invention but the invention 'is'not restricted to theseexan ples. The parts are I We have found that very valuable vat dyestuffs are obtained. layreacting at least one of the halogens chlorine and bromina'oragents supplying these halogens, in a halogen *sulje' phonic acid, in particular chlorsulphonic acid, 1 with dibenzanthrone, isodiben'zanthrone or, their halogen substitution products, inthe presence of a considerable amount of sulphur. ,The amount of sulphurshould beat least about 2 per cent, preferably betweenaboutB and about 12 per cent, of the mixture of dibenza-nthrone 5 or" the like and halogen sulphonic acid' subjected to the reaction. Instead of sulphur, a-

corresponding amount of substances supplying sulphur, as for example sulphur 'monochioride,

maybeemployed. Reactionalready sets in at 80 ordinary temperature; but it is accelerated by-increasing thetemperature to betweenabout 403' gandabout 60 C. Higher temperatures such as to 80 (3. may also be employed, but the temperature should notbe sohigh thatjsulphon-a tion takes placelfI-Ialogenation catalysts, such as iodine,- may be "added to the reaction mixture. Generally speaking,- unsubstituted diben'l- "zanthrone" or v i sodibenzar'ith'r'ene are used as initial materials, but halogenated dibenzanthrones 30 or isodibenzanthronessuch as are prepared by halogenation in organicsolvents, for "exarn'ple ni- -trobenzene, or in sulphuric or chlorsulphonic acid, maybeused'as well' and their propertiesimproved. The new dyestufis I contain, in addition to; h'alogen,-from about 3 to"about 12 per centofsulphur, in a chemically combined state,

: :he'ri carrying out th V halog'enation chloi'f sulphonic acid, the latter gives ofisome chlorine to the products. Especially valuable product's arethose obtained by means of bromine in chlor- 5 sulphonic'acid,oontaining betWeenaliout ZO and "about 24pm cent of T bromine and some' chlorine, preferably-between about l and abo'ut 3 percent,

, andslulphur in'the before-mentionedamounts,

preferably between abou'tffi and about 10 percent. #Ihenewdyestuffs have excellent tinctoria'l and fastne'ss properties, in'particular they are insensitive to the temperatureemployed in dyeing, i. e.

:.:they' give. the sameshades whether dyedat high-. er or lower temperatures, and against drops-of Mater. Z Ihe dyeings obtainable'irom these dye- The following examples will further 'illustrate by weight. H Example 1 vin fioflgpartsj of chlorsulphonicj, acid at room 7 temlfl'parts'of pluredibenzanthroneiare dissolved taken place, 40 parts of sulphur andQZO parts of bromine are added. Tf1eso1ution is heated grad esnym CQw-ithin from 3 to 5 hours and{ stirred at the s aid temperature until bromine ,isno longer absorbed. After cooling-the reacftion imixtiire' it is poured onto ice, dilutedwith water; boiled, filtered and washed with water until neutral, Aidark paste, is obtained which (yields with caustic soda solution andhydrosuh ,iihite a red h blu t fr m hi e etab ,ribresare dyed seamen nayy blu'eshades of vl'erygood ia'stne'ss' properties. When-' dried the dyestuff is adark powder whichdissolyes inconcentrated sulphuric acid giving a reddish ,blue

coloration; V e 1 V The crude dyestufi is somewhat contaminated with sulphur which'm'ayjbe-removedif, n es-,

sary by the'tusuallmethods; as for example by "boiling up withxcarbon disulphide. *Thedystuff qfreedfr'o'in free sulphur"containsfacc'ording to ,anaiysisjaboiit 22 percent of bromine, about 3 lpercent of chlorine and about 8 per cent "of"sulpliur. .The'content of the dyestufi othalog'tenand .combined sulphur varies withlthereaction eonditions whichmay be varied within very- :wide

limits. Thus instead of raising the said reaction temperature unto 50 .Cjit may beraised ,some :what higher and the durationflof the reaction shortened, orlowerirreaction temperaturegmay 1 ,be usedandtheirleaction time lengthened, orail 5 the/working conditions be 5 changed famon'g which are included the amount .ofssulphuri'and bromine added. "Inthis way navy-blue dyestuffs -may be obtained which-yield more reddishi'or more greenish'dyeings depending on the working f conditions. y o

' E em lar,

50 parts of-dibenzanthrone are dissolved in" 300 parts of ehlorsulphonicacid andf30'parts of -su1 Jphur'and 25 parts of bromine areaddedthereto. The, procedure described; in Example-l is then followed. 'I'he-res'ultingdyestufbm a" dark-powder which hissolves in' concentrated sulphuric acid 'giving a reddish-violet coloration. With caustic OFFICE?" 2012,558 e f g *rine ior chlorine soda solution and hydrosulphite, a red-violet vat is obtained from which vegetable fibres are dyed fast navy-blue shades,

about 7 percent of sulphur'and has the property,

remarkable for a navy-blue dyestufi .of. this class,

that it is not sensitive to temperature during dyeing, i. e. the shades of the dyeings obtainedat: difierent, temperatures, aslfor example 50? and 70 0., arepractically'identical. V Example 3 25 parts of dibenzanthrone are dissolved in 200 parts of chlorsulphonic, acid.*- 20 parts of 'sulphur are added and chlorine led in, the tempera- I time being gradually raised to 50 C, during from 3 to hours. When .this temperatureisreached,1 chlorine'is still led in at from 50 to 52 C. .until from to 17 parts of chlorine have; been ab.- scrbed in alIQj Ihe reactionmixture is worked up in the usual manner. A dark paste is thuso btain e d which yields a blue vat from which vegetables'fibres are dyed fast navy-blue shades. In. ,the dry state, the dyestufi is a dark powder which dissolves in concentrated sulphuric acid giving a blue coloration. By extraction with carbon disulphide, the powder may be freed from admixed" su1phur; 'itthenhas; according to analysis, a. chlorine content of l'3'per cent and a'sulphur contentof 12 per cent. v V 1 I If 'more chlorniethan specifiedbe led into the reaction mixture, dyestuffs having stillfhig her contents of chlorine are obtained, which yield more greenish dyeings.

A bromination may also becombined with the chlorination, by adding to the reaction-mixture beiore leading in the chlorine a certain amount sulphur: V r 1 Emm q 50 parts of pure isodibenzanthrone are heated in themanner. described in Example 1 with .400 parts of chlorsulphoniclacid; .40 parts of sulphur land;25 parts ,ofpbromine; A crystalline paste having-aabronze lustresis obtained which. yields a blue gvat from-which vegetable'fibres are dyed very fastrand beautiful violet blue shadesjThe d-yeings havea fastness to drops of water which is comparatively good fora dyestufi. of the .is'odi- .benzanthrone series: In theidrystate'thei dyestuff isxapo-wder having a bronze lu'streyyhich' dissolvesin concentrated sulphuric acid giving a greencoloration, .Theydyestufi-when freed from admixed sulphur, contains about 4 percent of sulphur, 22 per cent of bromine-andl per cent of chlorinegaccording'to analysis 7 Similar dyestuffs are-obtained bycausing chloandbromine to. act on isodiben- .zanthrone. o f a I 'QEmample 5 25 parts of pure dibenzanthrone are dissolved in 200 parts of chlorsulpho-nic acid; .20. parts of finely pulverized potassium bromide rare intro- ,duced at about 15. C.; parts of sulphur, are .added and the whole heated' in' the manner-de- {scribed in- Example :1. A dyestuff is obtained ,1whichpis verysimilar inits tinctorial an'dchemi- ,cal properties to. that. described Examplegl.

The purified dyestuff contains, according to analysis, about 22 per cent of bromine, about 2 per cent of chlorine and r m after: the addition of 025 part of Sulphur as described in Example 1.

:chlorsulphonic' acid.

Example 6 20 parts of monobromdibenzanthrone (obtainablebyreacting 50 parts of dibenzanthrone in 400 parts of chlorsulphonic acid with 10 parts of for fi'hours at about 40 C.) are dissolved in 160 parts of chlorsulphonic acid whereupon 20 parts of sulphur and 8 parts-of bromine are added and 'the whole slowly heated to 60 C. and stirred at v the said temperature for several hours. The reaction isterminated when on working up and dyeing of several samples a difference in shade ean "no more be observed. The reaction mixture is then worked up in theusual manner. The resulting dyestuff ispractically identical as regards its reactions and fastness properties with the dyestuff obtained according to Example 1.

Example 7 of between 5 and 6'hours to 50 C. and stirred at the. said temperature until all bromine is cons nned, The reaction mixture iis-then worked up The productvis a dark powder after removing the adherent sulphur and is very similar in its chemical and tinctorial properties to the dyestuffs described in Examples 1 and 2. According to analysis it con- .tains about 20 to 21 per cent of bromine,,about 1.;A process of producing .vat dyestuffs which comprises reacting a compound selected from the group consisting of dibenzanthrone, isodibenzanthroneand their halogen substitution products,

in ahalogen s ulphonic acid with a halogenating ;agent; selected from the 7 group consisting of .chlorine, bromine andagents supplying these hal- .comprisesreacting a compound selected from the group consisting of dibenzanthrone, isodibenzanthrone andtheir, halogen. substitution products, in chlorsulphonic acid with ahalogenating agent. se-

lected from, the groupconsisting of chlorine, bromine and agents supplyingthese halogens in the 'presenceofat least twoper cent of sulphur :by weight'of the mixture of, the said compoundand 3.[Apro cess ofproducing vat dyestuffs which comprises reacting dibenzanthrone in chlorsulphonic'acid with brominein the presenceof at .leasttwo per cent by weight'of sulphur of the .mixture of the said dibenzanthrone andchlorsulfphonicacld. V

4.,A process ofproducing vat dyestuffs which comprisesreactinga compound selected from the group consisting of dibenzanthrone, isodibenzan- .throne and theirhalogen; substitution products, in ,chlorsulphonic. acid at between about 40'and about .6090; with a halogenating agent selectedfrom the j group consisting of chlorine, bromine and agents supplying'these halogens, and in the presence of .atleast two per cent .of sulphur, by weight of the -mixture of the said compound and chlorsulphonic -;acid. j

5, Aprocessof-producing vat dyestufiswhich 76 comprises reacting dibenzanthrone inchlorsulphonic acid at between about 40 and about C. with bromine and in the presence of at least two per cent of sulphur by weight of the mixture.

of the said dibenzanthrone and chlorsulphonic acid. 7 a a 6.- Vat dyestufi's which are halogen substitution products of a compound selected from the group consisting of dibenzanthrone, and isodibenzanthrone, containing atleast one of the halogens chlorine and bromine and from about 3 to about'12 per cent of sulphur, dyeing the vegetable fibre from green-blue to violet-blue shades.

7. Vat dyestuffs which are halogen substitution products of a compound selected from the group consisting of dibenzanthrone and isodibenzanthrone, containing at least one of the halogens chlorine and bromine and from about 5 to about 10 1 'fibre per cent of sulphur, dyeing the vegetable from green-blue to violetblue shades. l

8. Vat dyestuffs which are halogen substitution products of a compound selected-from the group consisting of dibenzanthrone and isodibenzan- I throne, containing chlorine and bromine and from about 3 to about 12 percent of sulphur, dyeing'the vegetable fibre from green blue to violet.- blue shades. V I

9. Vat dyestuffs which are halogen substitution products of a compound selected from the group consisting vof dibenzanthrone and isodibenzanthrone containing chlorine and bromine and a from about 5 to aboutlO-percentof sulphur, dye- Y ing vegetable fibre from green-blue to violet-blue shades;

l chlorine and about 7 per cent of sulphur, dissolving in concentrated sulphuric acidto give a red- 7 1 r I 10. .Vat dyestufis which are dibenz anthrones containing Irom'about 20 to about;24 per cent of bromine, chlorine and from abouti5 to about 10f I per centoi sulphur, Idyeing thevegetable fibre navy-blue shades.

sulphur, dyeing shades; a V v 12. Bromo chlorodibenz anthrone" containing fibre navy-blue shades'irom' a reddish-blue vat.

13. Bromo chlorodibenzanthrone containing 2 1 about 22 per cent oi bromine, about 3 per cent of i chlorine and about ,8- per cent of sulphur dissolving indconcentrated sulphuric acid to give a redis I dish-blue coloration and. dyeing the vegetable about 22 per cent of bromina about 2 percent of dish violet colorationand dyeing thelvegetable 1 fibre navyt-bluershades from a red-violet vat.

14. Bromo chlorodibenzanthrone containing I about 20'to 21: percent of bromine, about 2.5 to3 per cent of chlorine and about'6 per centof sulphur, dissolving in concentrated sulphuric acid.

v.to give a reddish-violet coloration and dyeing the vegetable fibre navy-blue shades 'froma red-vio- I v H GQWOIJ'FH: 

